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Despite significant progress in aliphatic decarboxylation, an efficient and general protocol for radical aromatic decarboxylation has lagged far behind. Herein, we describe a general strategy for rapid access to both aryl and alkyl radicals by photosensitized decarboxylation of the corresponding carboxylic acids esters followed by their successive use in divergent carbon-heteroatom and carbon-carbon bond-forming reactions. Identification of a suitable activator for carboxylic acids is the key to bypass a competing single-electron-transfer mechanism and "switch on" an energy-transfer-mediated homolysis of unsymmetrical σ-bonds for a concerted fragmentation/decarboxylation process., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The development of new hydrogen-atom transfer (HAT) strategies within the framework of photoredox catalysis is highly appealing for its power to activate a desired C-H bond in the substrate leading to its selective functionalization. Reported here is the first photoredox-mediated hydrogen-atom transfer method for the efficient synthesis of ynones, ynamides, and ynoates with high regio- and chemoselectivity by direct functionalization of Csp2 (O)-H bonds. The broad synthetic application of this method has been demonstrated by the selective functionalization of C(O)-H bonds within complex molecular scaffolds., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)